Quaternary ammonium salts



United States Patent QUATERNARY AMMONIUM SALTS John P. Conbere andEdward M. Perry, Barrington, R. 1., assignors to Arnold, Hoffman & 'Co.,Incorporated, Providence, R. I., a corporation of Rhode Island NoDrawing. Application September 6, 1956 Serial No. 608,187

Claims. (Cl. 260-4045) The present invention relates to novel quaternaryammonium compounds and methods of preparing the same.

An object of the invention is to provide novel quaternary ammonium saltsof fatty acid esters of a polyhydroxypolyamine.

An additional object is to prepare novel compounds useful to impartsoftening and lubricating characteristics to textiles.

A further object is to prepare novel textile softeners having increasedstability to heat. i,

Yet another object is to prepare novel anti-static agents for textiles.

Still further objects and the entire scope of applicability of thepresent invention will become apparent from the detailed descriptiongiven hereinafter; it should be understood, however, that the detaileddescription and specific examples, while indicating preferredembodiments of the invention, are given by way of illustration only,since various changes and modifications within the spirit and scope ofthe invention will become apparent. to those skilled in the art fromthis detailed description.

It has been discovered that these objects can be attained by thepreparation of quaternary ammonium salts of fatty acid esters ofN,N,N',N'-tetrakis(2 hydroxyethyl)ethylenediamine having the formula110011.011: crnomon z or the formula where R is an aliphatic acylradical having :12 to 18 carbon atoms or hydrogen, at least one R beingan aliphatic acyl radical, M is a monovalent hydrocarbon groupcontaining 1 to 4 carbon atoms, X is ananion and Z is the valence of X.

R can be lauroyl, stearoyl, oleoyl, myristoyl, palmitoyl, ricinoleoyl,etc. M can be methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl. X canbe a sulfate ion, a halide ion, e. g., chloride, bromide, iodide,benzene sulfonate ion, toluenesulfonate ion, borate ion, phosphate ion,etc. When there are 2 M groups, they can be alike or different.Similarly, when more than one R is an acyl group, the acyl groups can bealike or different.

The compounds of the present invention are valuable as softening andanti-static agents for textile fabrics such as cellulose acetate, nylon,vinyl resins, e. g., vinyl chloride resins, etc. I a I The compounds ofthe present invention lend valuable softening and lubricity to textilefabric and also prevent the undesirable physical manifestation of staticelectrical charges which tend to accumulate on many fibers. Thecompounds are water dispersible which results in easy and low costapplication. The compounds also are unique "ice in that they afford ameans of binding three or four long fatty acid chains, which whenquaternized possess unexpected solubility and compatability inconventional aqueous textile resin treating baths with internal pHbuifering. Such buffering is necessary for urea and melamineformaldehyde resin bath stability.

The present products also haveinherent stability to heat (non-scorching)which is superior to the nonquaternized acetate salts of the samestarting compound, for example.

The compounds of the present invention are made by reacting theappropriate tertiary amine with a quaternizing agent. As quaternizingagents, there can be employed alkyl halides, e. g., methyl bromide,methyl chloride, methyl iodide, ethyl bromide, propyl chloride, n-butylchloride, dimethyl sulfate, diethyl. sulfate, di-npropyl sulfate,di-n-butyl sulfate, methyl benzene sulfonate, methyl p-toluenesulfonate,ethyl p-toluenesulfonate, butyl p-toluenesulfonate, trimethyl phosphate,tributyl phosphate, dimethyl butyl phosphate, trimethyl borate, allylchloride, allyl bromide, crotyl chloride, etc.

Whether the mono or diquaternary ammonium salt is formed depends on theproportions of the tertiary amine and the quaternizing agent. Twoequivalents of quaternizing agent are required to form the diquaternarycompound and only one equivalent to form the monoquaternary compound.

As illustrative compounds of the present invention, there can bementioned the monoquaternary ammonium salt prepared fromN,N,N',N-tetrakis(Z-hydroxyethyl) ethylenedia-mine -monostearate anddimethyl sulfate, the corresponding salt from diethyl sulfate, thecorresponding salt from methyl bromide, the corresponding salt fromdi-nbutylsulfate, the corresponding salt from di-n-propyl sulfate, thecorresponding salt from metyl chloride, the corresponding salt frommethyl bromide, the corresponding salt from methyl iodide, thecorresponding salt from ethyl bromide, the corresponding salt fromn-propyl bromide, the corresponding salt from n-butyl bromide, thecorresponding salt from isobutyl chloride, the corresponding salt fromtributyl phosphate, the corresponding salt from trimethyl phosphate, thecorresponding salt from trimethyl borate, the corresponding salt frommethyl benzenesulfonate, the corresponding salt from methylp-toluenesulfonate. In place of the monoquaternary ammonium salt, therecan be prepared the corresponding diquaternary compound, e. g., thediquaternary ammonium salt prepared fromN,N,N',N'-tetrakis(2-hydroxyethyl) ethylenediamine monostearate anddimethyl sulfate. Similarly, there can be made the monoquaternaryammonium salt prepared fromN,N,N,N-tetrakis(2-hydroxyethyl)ethylenediamine distearate and. dimethylsulfate, as well as of the other quaternizing agents set forth supra.The diquaternary salt of this compound, e. g., with dimethyl sulfate,also can be made. Likewise, there can be made the monoquartenaryammonium salt prepared fromN,N,N,N-tetrakis(Z-hydroxyethyl)ethylenediarnine tristearate anddimethyl sulfate, as well as of the other quaternizing agents set forthsupra. The diquaternary stalt of this compound, e. g., with dimethylsulfate, also can be made. Additionally, there can be made themonoquaternary ammonium salt prepared from N,N,N',N-tetrakis(Z-hydroxyethyl)ethylenediamine tetrastearate and dimethyl sulfate, :aswell as of the other quaternizing' agents set forth supra. Thediquaternary salt of this compound, e. g., with dimethyl sulfate, alsocan be made.

In place of the stearate compounds, compounds containing any of the acylgroups previously set forth can be made. Additionally, mixed acyl groupcontaining compounds can be prepared.

amine fatty acid ester productsare oils or waxes. Increas ing the numberof acyl'groups in the molecule gives a harder wax.

Illustrative examples showingthe preparation of the starting materialsfor the present invention are-given.

below.

EXAMPLE 1 N ,N ,N ',N '-letrakis(Z-Izydroxyethyl ethylenediam inemonostearate A mixture of 472 g. of N,N,N',N-tetrakis(2-hydroxyethyl)ethylenediamine, 680 g. n-butyl stearate and 2.9 g. sodiumhydroxide was stirred and heated to 110 C. at 70 mm. pressure. n-Butylalcohol began to distill from the reaction mixture. The temperature wasraised to 140 C. during an hour. The pressure was then reduced to 17 mm.and the charge stirred at 140/ 17 mm. for one hour and fifteen minutesto remove the last' traces of n-butyl alcohol. A total of 151 g. ofbutyl alcohol was collected (theory 148 g.). The product was a softtanwax which contained 2.95 atoms of active hydrogen per mol.

EXAMPLE 2 N ',N ,N ',N -tetrakis(Z-hydroxyethyl ethylened faminedistearate' A stirred mixture of 78.6 g. of N,N,N.,N'.-tetrakis(2-hydroxyethyl)ethylenediamine, 204 g. of n-butyl stean ate and 0.7 g.of sodium hydroxide was heated to 120 C. at 70 mm. n-Butyl alcohol beganto distill from the reaction mixture. The temperature was raised to 140C. during one hour. The pressure was then reduced to 20 mm. and thecharge stirred at 140 C. for one-half hour. A quantitative yield ofproduct containing 2.0 atoms .of active hydrogen per mol was obtained.

EXAMPLE 3 N,N,N,N'-tetrakis(ZrhydrOxyethyZ) ethylenediamine tristearateA stirred mixture-of .236 g."N,N,N.',N'-tetrakis::(2-hydroxyethyl)ethylenediamine; 1020 g. of n-butylstearate and 3.1 g; of sodium hydroxide was heated at 70 mm.

until n-butyl alcohol began to distill at 106 C. Thetemperature wasmaintained at 110 C. and the presssure at 70 mm. for one hour whilen-butyl alcohol was collected. The temperature was gradually raised to140 C. and then the pressure was reduced to 20 mm. Thereaction mixturewas stirred at these conditions for one and one-half hours. The productwas obtained as a wax on cooling.

EXAMPLE 4 N ,N ,N ,N '-tetrakis(2-hydroxyethyl ethylenediaminetetrastearate EXAMPLE 5 N ,N ,N ',N '-tetrakis( Z-hydroxyethylethylenediamine dioleate In a similar manner to' Example -3, 11.8 g. of

N,N,N,N tetrakis Z-hydroxyethyl ethylenediamine :was

4 treated with 33.8 g. of n-butyl oleate and 0.2 g. of sodium hydroxideto yield N,N,N,N-tetral is(2-hydroxyethyl) ethylenediamine dioleate as adark viscous liquid.

EXAMPLE 6 N ,N ,N 'N -tetrakis (Z-hydroxyethyl ethylenediaminedilaurate- In a similar manner to Example 3, 236 g. of N,N,N',N-tetrakis(2-hydroxyethyl)ethylenediamine was treated with 512g. n-butyllaurate and 1.9 g. of sodium hydroxide to. yieldN,N,N',N-tetrakis,(2-hydroxyethyl) ethylenediamine dilaurate as a lowmelting wax.

The compounds ofthe present invention are. prepared as follows:

EXAMPLE 7 Monoquaternary ammonium salt prepared from N,N,

N ,N -tetrakis( Z-hydroxyethyl ethylenediamine monostearate and dimethylsulfate N,N,N',N' tetrakis(2 hydroxyethyl)ethylenediamine monostearate(150.6 g.) was heated to C. and 37.8 g. of dimethyl sulfate added slowlywith stirring. The temperature was maintained between 100 C. and C. andheld there for two hours. A soft wax, easily dispersible in water, wasobtained.

EXAMPLE 8 Monoqualemary ammonium salt prepared from N,N,

N ,N -tetrakis(Z-hydroxyethyl) ethylenediamine monostearate and dimethylsulfate in aqueous solution A stirred mixture of 72 g. ofN,N,N,N'-tetrakis(2- hydroxyethyl)ethylenediamine monostearate and 150ml. of water was heated to 100 C. and 18 g.'of dimethyl sulfate wasslowly added. The mixture was heated at 100 C. forfive hours and thencooled to room temperature to yield a water dispersible product.

EXAMPLE 9 Monoquaternary ammonium salt prepared from N,N;

N ,N -tetrakis(Z-hydroxyethyl ethylenediamine monostearate and methyltoluenesulfonate N,N,N,N' tetrakis(2 hydroxyethyl)ethylenediaminemonostearate (150.6 g.) was heated to 110 C. and 55.8 g. of methyltoluenesulfonatewas slowly added with stirring. The temperature wasincreased to and maintained at C. for four hours, A water dispersibleproduct was. obtained.

EXAMPLE 10 Monoquaternaryammonium salt prepared. from N,N,

N,N'-tetrakis(2 hydroxyethyl)ethylenediamine distearate and dimethylsulfate N,N,N',N"- tetrakis(2 hydroxyethyl) ethylenediamine distearate(153.6 g.) was heated to 130 C. and 25.2 g. ofdimethyl'sulfate wasslowly added. After the addition was complete, the whole was maintainedat 130 C. for an additional hour anda half. The product was a waterdispersible wax.

EXAMPLE 11 D'iquaternary ammonium salt prepared from N,N,N',N-

tetrakis(2-hydroxyethyl) ethylenediamine distearate and dimethyl sulfateDimethyl sulfate (50.4 g.) was added slowly with stirring to 153.6 g. ofN,N,N,N'-tetrakis(2-hydroxyethyl) ethylenediamine distearate at 130 C.The. heating was continued after the addition-was complete for anadditional-:two hours. The-product was a hard wax and may be dispersedin water.

EXAMPLE 12 M onoquaternary ammonium salt prepared from .N,N.

N. .,N '-tetrakis(2.- hydroxyethyl) ethylenea'iamine distearate andmethyl toluenesulfonate N,N,N ,N.' tetrakis(2hydroxyethyDethylenediamine idi'stearate (153.64g) was-heatedto 130 C.,and 37.2 g.

of methyl toluenesulfonate was slowly added with stirring. After theaddition was complete, the mixture was heated for four hours at 130 C.The product was a water dispersible wax.

EXAMPLE 13 Monoquaternary ammonium salt prepared from N,N,

N,N-tetrakis(2 hydroxyethyl)ethylenediamine distearate and methylbromide Monoquaternary ammonium salt prepared from N,N,

N,N-tetrakis(2 hydroxyethyl)ethylenediamine tristearate and dimethylsulfate 206.8 g. of N,N,N',N'-tetrakis(2-hydroxyethyl)ethylenediaminetristearate was heated to 127 C., and 25.2 g. of dimethyl sulfate slowlyadded with stirring. After the addition was complete, the temperaturewas maintained at 125 to 130 C. for three and one-half hours. Theproduct was a hard wax that dispersed in water. The product calculatedfor C64H125N207: N, 2.41.

Found: N, 2.3. Quaternary ammonium salt 98%; free dimethyl sulfate, nonedetectable.

EXAMPLE 15 Monoquaternary ammonium salt prepared from N,N,

N ',N-tetrakis(2 hydroxyethyl)ethylenediamine dilaurate and dimethylsulfate 120 g. of N,N,N,N'-tetrakis(2-hydroxyethyl)ethylenediaminedilaurate was heated to 65 C. and 25.2 g. of dimethyl sulfate was slowlyadded with stirring. After all of the dimethyl sulfate had been added,the mixture was heated to 130 C. for three hours. The product was a lowmelting wax that formed a dispersion with water.

EXAMPLE 16 Monoquaternary ammonium salt prepared from N,N, N ,N-tetrakis(Z-hydroxyethyl )ethylenediamine dioleate and dimethyl sulfate152.8 g. of N,N,N',N-tetrakis(2-hydroxyethyl)ethylenediamine dioleatewas heated to 65 C., and 25.2 g. of dimethyl sulfate slowly added withstirring. After the addition was complete, the temperature was increasedto and maintained at 130 C. for three hours. The product was a viscousliquid that formed a dispersion in water.

EXAMPLE 17 Monoquaternary ammonium salt prepared from N,N,

N',N' tetrakis(2 hydroxyethyl)ethylenediamine distearate and allylchloride Allyl chloride (15.2 g.) was slowly added to 153 g. ofN,N,N',N'-tetrakis(2 hydroxyethyl)ethylenediamine distearate which hadbeen warmed to 60 C. After the addition was complete, the whole washeated at 100 C. for one hour to yield the product as a soft, waterdispersible wax.

EXAMPLE 18 Monoquaternary ammonium salt prepared from nbutyl bromide andN,N,N,N'-tetraki (Z-hydroxyethyl) ethylenediamine distearate n-Butylbromide (27.4 g.) was "added slowly to a stirred melt of 153 g. ofN,N,N,N'-tetrakis (Z-hydroxyethyl)ethylenediamine distearate at 100 C.When the addition was complete, the reaction mixture was stirred andheated at 120 C. for an additional three hours and thirty minutes. Theproduct was a water dispersible wax.

EXAMPLE l9 Monoquaternary ammonium salt prepared from N,N,

N',N' tetrakis (2 hydroxyethyl)ethylenediamine tetrastearate anddimethyl sulfate Dimethyl sulfate (6.3 g.) was slowly added to 65 g. ofN,N,N,N' tetrakis(2-hydroxyethyl)ethylenediamine tetrastearate at C.After the addition was complete, the whole was stirred and heated at 100C. for one hour to yield a water dispersible wax.

The quaternary ammonium salts of the present invention are waterdispersible and possess surface active properties. They are easilyapplied to fabrics by the usual padding methods from aqueousdispersions. A typical example illustrating this use is as follows:

EXAMPLE 20 A 0.30% dispersion of the monoquaternary ammonium saltprepared from N,N,N,N-tetrakis(2-hydroxyethyl)ethylenediamine distearateand dimethyl sulfate was applied to Nylon 200 taffeta by standardpadding techniques, i. e., a conventional padding machine, at F. in sucha manner as to result in 50% pickup of the dispersion by the fabric. Thefabric was dried at 225 F. Nylon 200 taffeta treated in this mannerpossessed improved softness to the hand, increased lubricity, andsuperior anti-scorch and anti-static properties. Nylon 200 is asynthetic linear superpolyamide of the hexamethyleneadipamide type.

Unless otherwise stated, all parts and percentages are by weight.

We claim:

1. A compound selected from the group consisting of ROCHzCHr CHzCHzOR Zwhere R is selected from the group consisting of aliphatic acyl radicalscontaining from 12 to 18 carbon atoms and hydrogen, at least one R beingsaid aliphatic acyl radical, M is a monovalent hydrocarbon groupcontaining l to 4 carbon atoms, X is an anion and Z is the valence of X.

2. A compound as recited in claim 1 wherein at least one R is a stearoylradical.

3. A compound as recited in claim 1 wherein at least one R is lauroyl.

4. A compound as in claim 1 wherein M is a saturated hydrocarbon group.

5. A compound as in claim 1 wherein M is an ethylenically unsaturatedhydrocarbon group.

6. A compound as in claim 1 wherein X is the sulfate ion.

7. A compound as in claim 1 wherein X is the toluenesulfonate ion. 1

8. A compound as in claim 1 wherein X is a halide ion. 9. A compound asin claim 1 wherein X is a chloride ion. 10. A compound as in claim 1wherein X is a bromide 1011.

and

References Cited in the file of this patent UNITED STATES PATENTS2,719,156 De Benneirille et al Sept. 17, 1955 FOREIGN PATENTS 678,604Great Britain Sept. 3, 1952 Notice of Adverse Deeisien in InterferenceIn Interference N0. 903% involving Patent No. 2,878,273, J. P. Conlbereand E. M. Perry, Quaternary ammonium salts, final judgment adverse tothe patentees was rendered Apr. 20, 1962, as to claims 14 and 6-10.

[Ofiiaz'al Gazette June 12,1962]

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF